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EP2132819B1 - Fuel cell system - Google Patents

Fuel cell system Download PDF

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Publication number
EP2132819B1
EP2132819B1 EP06851562A EP06851562A EP2132819B1 EP 2132819 B1 EP2132819 B1 EP 2132819B1 EP 06851562 A EP06851562 A EP 06851562A EP 06851562 A EP06851562 A EP 06851562A EP 2132819 B1 EP2132819 B1 EP 2132819B1
Authority
EP
European Patent Office
Prior art keywords
fuel
hydrogen
gas
fuel cell
circulation pump
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP06851562A
Other languages
German (de)
French (fr)
Other versions
EP2132819A2 (en
Inventor
Shinichi Makino
Masatoshi Iio
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Publication of EP2132819A2 publication Critical patent/EP2132819A2/en
Application granted granted Critical
Publication of EP2132819B1 publication Critical patent/EP2132819B1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04231—Purging of the reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04225—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during start-up
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
    • H01M8/04302—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during start-up
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0432—Temperature; Ambient temperature
    • H01M8/04358—Temperature; Ambient temperature of the coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0438—Pressure; Ambient pressure; Flow
    • H01M8/04388—Pressure; Ambient pressure; Flow of anode reactants at the inlet or inside the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0438—Pressure; Ambient pressure; Flow
    • H01M8/04395—Pressure; Ambient pressure; Flow of cathode reactants at the inlet or inside the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0444—Concentration; Density
    • H01M8/04455—Concentration; Density of cathode reactants at the inlet or inside the fuel cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
    • H01M8/04544—Voltage
    • H01M8/04559—Voltage of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
    • H01M8/04574—Current
    • H01M8/04589—Current of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04701—Temperature
    • H01M8/04723—Temperature of the coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04701—Temperature
    • H01M8/04731—Temperature of other components of a fuel cell or fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow of fuel cell reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04761—Pressure; Flow of fuel cell exhausts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04768—Pressure; Flow of the coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a proton exchange membrane fuel cell system and a method for starting up a fuel cell system.
  • a control value of a secondary pressure regulator is set to be higher than a supply pressure in a normal power-generating state and hydrogen is supplied to the fuel cell by opening a hydrogen supply solenoid valve while driving a hydrogen pump.
  • a fuel cell system includes an air-replacement-state recognizing unit including at least one of a timer, oxygen concentration sensor and a fuel-gas concentration sensor being disposed at a portion, where replacement by air is finished first or last in the fuel electrode, for estimating or detecting a state in which hydrogen and air are unevenly distributed in at least one of a fuel electrode and a fuel-gas circulation path and a start control device for operating the fuel-gas circulation pump after supplying the fuel gas upon starting the fuel cell if the air-replacement-state recognizing unit estimates or detects that hydrogen and air are unevenly distributed.
  • the timings of activation of the fuel-gas circulation pump and the supply of fuel gas are changed on the basis of the air replacement state and, as a result, deterioration of the fuel cell caused by uneven distribution of the fuel gas and air in the fuel electrode caused by air infiltration into the fuel chamber (the fuel electrode, the fuel-gas circulation path, and fuel-gas circulating means) is prevented.
  • Fig. 1 is a diagram illustrating the fuel cell system
  • Fig. 2 which is a diagram illustrating a single cell in a fuel cell.
  • a single cell 100 of a fuel cell includes a membrane-electrode assembly (MEA) 101 including a solid polymer electrolyte membrane 102, a fuel-electrode catalyst layer 103 provided on one side of the electrolyte membrane 102, and an oxidizer-electrode catalyst layer 104 provided on the other side of the electrolyte membrane 102; a fuel-gas diffusion layer 105 provided on one side of the MEA 101; an oxidizing-gas diffusion layer 106 provided on the other side of the MEA 101; and separators 107 and 108.
  • MEA membrane-electrode assembly
  • a fuel-gas path 109 is provided between the separator 107 and the fuel-gas diffusion layer 105 and an oxidizing-gas path 110 is provided between the separator 108 and the oxidizing-gas diffusion layer 106.
  • the fuel cell body includes a plurality of cells similar to the single cell 100. Fuel gas (hydrogen) and oxidizing gas (air) are externally supplied to the fuel cell body and are caused to flow through the fuel-gas path 109 and the oxidizing-gas path 110, respectively, so that electric power is generated as a result of electrochemical reaction.
  • a fuel cell system to which the present invention may be applied includes a fuel cell body 1, an air system for supplying air, a hydrogen system for supplying hydrogen, a cooling water system for supplying cooling water, and a load system for extracting the electric power from the fuel cell body 1.
  • the air system includes an air compressor 11 for sucking in and compressing air, an air-system humidifier 13 for humidifying the air compressed by the air compressor 11 and supplying the humidified air to an oxidizer electrode 1a, an air pressure gage 16 for detecting the pressure of the air supplied to the oxidizer electrode 1a, and an air pressure regulator 15 for adjusting the pressure in the oxidizer electrode 1a by regulating the air discharged from the oxidizer electrode 1a.
  • the air compressed by the air compressor 11 is supplied through the air supply path 12 to the air-system humidifier 13, and is humidified. Then, the humidified air is supplied to the oxidizer electrode 1a of the fuel cell body 1, and is consumed by the electrochemical reaction in the fuel cell body 1. Then, the exhaust air is caused to flow through the air discharge path 14 and is discharged from the system after the pressure adjustment is performed by the air pressure regulator 15.
  • the pressure of the air supplied to the oxidizer electrode 1a is detected by the air pressure gage 16 disposed at an inlet of the oxidizer electrode 1a, and the air pressure regulator 15 is controlled such that the detected pressure becomes equal to a desired pressure.
  • the air-system humidifier 13 may include a water vapor exchange membrane for utilizing moisture included in the exhaust or may use pure water that is externally supplied.
  • a hydrogen detector 17 for detecting hydrogen included in the exhaust air is disposed downstream of the air pressure regulator 15. Accordingly, hydrogen that enters through the electrolyte membrane 102 from the fuel electrode to the oxidizer electrode and hydrogen that leaks from a sealed portion can be detected.
  • the hydrogen system includes a high-pressure hydrogen tank 21 that stores hydrogen gas, a hydrogen pressure regulator 23 for adjusting the pressure of the hydrogen, a hydrogen-system humidifier 25 for humidifying the hydrogen after the pressure thereof is adjusted and supplying the humidified hydrogen to a fuel electrode 1b, a hydrogen pressure gage 29 for detecting the pressure of the hydrogen supplied to the fuel electrode 1b, a hydrogen circulation pump 24 and a hydrogen circulation path 26 for circulating the hydrogen discharged from an outlet of the fuel electrode 1b to an inlet of the fuel electrode 1b, and a hydrogen discharge path 27 and a hydrogen discharge valve 28 for discharging impurities accumulated in the fuel electrode 1b and the hydrogen circulation path 26 from the system.
  • the hydrogen supplied from the high-pressure hydrogen tank 21 flows through the hydrogen supply path 22 via the hydrogen pressure regulator 23, where the pressure of the hydrogen is adjusted to a desire pressure, and joins the discharge hydrogen circulated by the hydrogen circulation pump 24. Then, the hydrogen is humidified by the hydrogen-system humidifier 25, and is fed to the fuel electrode 1b of the fuel cell body 1.
  • the pressure of the hydrogen supplied to the fuel electrode 1b is detected by the hydrogen pressure gage 29 provided at the inlet of the fuel electrode 1b, and the hydrogen pressure regulator 23 is controlled such that the detected pressure becomes equal to the desired pressure.
  • the excess hydrogen is caused to pass through the hydrogen circulation path 26 by the hydrogen circulation pump 24 and is used for power generation again.
  • the cooling water system is provided to maintain the temperature of the fuel cell body 1 at an adequate temperature by removing heat generated as a result of power generation performed by the fuel cell body 1.
  • the cooling water system includes a cooling water pump 31 for circulating the cooling water, a cooling water circulation path 32, a heat exchanger 33 for dissipating heat to the outside of the system, and a cooling water thermometer 34 for detecting the temperature of the cooling water at a position near a cooling-water outlet of the fuel cell body 1.
  • the cooling water is pressurized by the cooling water pump 31 so as to flow through the fuel cell body 1, and thereby absorbs heat. Then, the cooling water flows through the cooling water circulation path 32 to the heat exchanger 33, where the heat is discharged to the outside of the system. Then, the cooling water is caused to flow through the fuel cell body 1 again by the cooling water pump 31.
  • the temperature of the cooling water is monitored by the cooling water thermometer 34 and is adjusted to a temperature appropriate for the power generation level provided by the fuel cell body by controlling the amount of air flow supplied to the heat exchanger 33 by a blower.
  • a load device 40 that absorbs the electric power generated by the fuel cell body 1 functions as, for example, an inverter for supplying electric power to a vehicle drive motor in a fuel cell vehicle.
  • a power generation voltage of the fuel cell body 1 is detected by a voltmeter 41 and a current supplied to the load device 40 from the fuel cell body 1 is detected by an ammeter 42.
  • a controller 43 operates as a start control device to control the overall operation of the fuel cell system including the fuel cell body 1.
  • the controller 43 includes, for example, a central processing unit (CPU), a read only memory (ROM) that stores control programs and control parameters, a working random access memory (RAM), and a microprocessor including an input/output interface.
  • CPU central processing unit
  • ROM read only memory
  • RAM working random access memory
  • microprocessor including an input/output interface
  • the controller 43 outputs control signals to the air compressor 11, the air pressure regulator 15, the hydrogen pressure regulator 23, the hydrogen discharge valve 28, the cooling water pump 31, and the load device 40 on the basis of detected signals obtained from the air pressure gage 16, the hydrogen pressure gage 29, the cooling water thermometer 34, the voltmeter 41, and the ammeter 42 in order to adjust the pressure, temperature, the amount of flow, and the load in the fuel cell body 1.
  • the state of the fuel chamber (the hydrogen supply path 22, the hydrogen circulation pump 24, the hydrogen-system humidifier 25, the fuel electrode 1b, and the hydrogen circulation path 26 that varies in a period from when the fuel cell system stops to when the fuel cell system is restarted will be described with reference to Figs. 3 , 4 , and 5 .
  • the hydrogen-system humidifier 25 is omitted.
  • the fuel chamber is filled with hydrogen provided before the power generation was stopped.
  • the amount of the original hydrogen that has been replaced by the infiltrated air is referred to herein as the air replacement state.
  • the time required for the air to fill the fuel chamber varies in accordance with the material, the thickness, the temperature, etc., of the MEA, but is generally about several hours.
  • the time period and rate in which the hydrogen is replaced with air varies in accordance with the material, the thickness, the temperature, etc., of the MEA, but is generally about several minutes to several tens of minutes.
  • the uneven distribution refers to the state in which hydrogen and oxygen (or gases having different hydrogen densities) exist separately within the fuel chamber.
  • the controller 43 includes an air-replacement-state estimator for estimating an air replacement state of the fuel electrode 1b and the hydrogen circulation path 26 when the fuel cell system is stopped.
  • the controller 43 controls the timings at which the operation of the hydrogen circulation pump 24 is started and the hydrogen pressure regulator 23 is opened to start supplying the fuel gas on the basis of the estimated air replacement state.
  • Step 01 it is determined whether or not a time elapsed after the previous stoppage is within a first predetermined time by referring to an air replacement state recognizing means (e.g., a timer 60).
  • an air replacement state recognizing means e.g., a timer 60.
  • the process proceeds to S06, where the supply of hydrogen is started and the hydrogen circulation pump 24 is activated.
  • the order in which the supply of hydrogen is started and the hydrogen circulation pump 24 is activated is not restricted. Accordingly, the supply of hydrogen may be started and the hydrogen circulation pump 24 may be activated at the same time.
  • the normal operation routine is a control routine for performing a normal operation. More specifically, in the normal operation, the air system, the hydrogen system, the cooling system, the load system, and the control system are operated in accordance with the load requirement of the system.
  • the uneven distribution refers to the state in which hydrogen and oxygen (or gases having different hydrogen densities) exist separately.
  • the hydrogen circulation pump 24 is activated to generate a negative pressure at the outlet of (and gas flow through) the fuel electrode 1b, and then the supply of hydrogen gas is started by executing a hydrogen supply start routine. Therefore, the time period in which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b is reduced and the deterioration is reduced. Then, the process proceeds to S05, where the normal operation routine is performed.
  • the first and second predetermined times for determining the mixed air state of the fuel chamber on the basis of the time elapsed after the previous stoppage until the restart will be described below.
  • an oxygen concentration sensor or a hydrogen concentration sensor is disposed at a certain position in the fuel chamber of an experimental fuel cell system and a variation with time in the concentration of oxygen or hydrogen after the fuel cell system is stopped is experimentally measured.
  • the first predetermined time is determined as a time period during which the oxygen concentration is equal to or less than a predetermined value (the hydrogen concentration is equal to or more than a predetermined value) and at which the deterioration does not progress even when the normal operation routine is started in the fuel chamber immediately after the fuel cell system is started.
  • the second predetermined time is based upon temperature and is determined as a time period required for the oxygen concentration to become equal to or more than a predetermined value (for the hydrogen concentration to become equal to or less than a predetermined value) at which the deterioration of the fuel electrode 1b does not progress even when the hydrogen circulation pump 24 is operated first in the fuel chamber.
  • the time rate at which the air enters from the oxidizer electrode 1a to the fuel electrode 1b depends on the temperature of the fuel cell body 1, and the transmission speed is increased as the temperature is increased. Therefore, an experiment of, for example, varying the fuel cell temperature detected by the cooling water thermometer 34 and measuring the variation with time in gas concentration in the fuel chamber is performed and a correction value (correction coefficient) shown in Fig. 7 is determined and stored in the controller in advance. The first and second predetermined times are multiplied by the correction value so that first and second predetermined times can be used as more accurate determination thresholds.
  • FIG. 8 is a system diagram showing the structure according to the second embodiment.
  • the structure according to the second embodiment is similar to that shown in Fig. 1 except an oxygen concentration meter 50 for measuring the oxygen concentration in the hydrogen circulation pump 24 is additionally provided as an air replacement state recognizing means.
  • a method for starting the fuel cell system according to the second embodiment will be described below with reference to a flowchart shown in Fig. 9 .
  • the controller 43 detects the change and follows the steps of the flowchart of Fig. 9 to start the fuel cell system.
  • a detection value of the oxygen concentration meter 50 is read and it is determined whether or not the oxygen concentration in the hydrogen circulation pump 24 is equal to or more than a predetermined value. If it is determined that the oxygen concentration is equal to or more than the predetermined value in S11, that is, if the result of the determination of S11 is Yes, it is determined that the fuel chamber is filled with air transmitted from the oxidizer electrode 1a during the stoppage (state B) and the process proceeds to S12.
  • the hydrogen circulation pump 24 is started to generate a negative pressure at the outlet of (and gas flow through) the fuel electrode 1b, and then the supply of fuel gas is started. Therefore, the time period in which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b is reduced and the deterioration is suppressed. The process then proceeds to S14, where the normal operation routine is performed.
  • State A and state C can be divided from each other on the basis of the time elapsed after the stoppage, as described in the first embodiment. Therefore, the start time may, of course, be reduced by immediately performing the normal operation routine if it is determined that the fuel chamber is in state A.
  • the predetermined value used for the determination performed in S11 is obtained in advance by experiment and is set to an oxygen concentration at which the deterioration of the fuel electrode 1b does not progress even when the hydrogen circulation pump 24 is operated first in the fuel chamber.
  • a gap between a casing and a rotor is set to be sufficiently small so as to prevent an internal leakage from an outlet to an inlet during operation. Therefore, the hydrogen circulation pump 24 cannot be easily filled with air compared to other portions after stopping, and is last to be filled with air in the hydrogen circulation system via diffusion.
  • Fig. 10 is a system diagram showing the structure according to the third embodiment.
  • the structure according to the third embodiment is similar to that shown in Fig. 1 except a hydrogen concentration meter 51 for measuring the hydrogen concentration in the hydrogen circulation pump 24 is additionally provided as an air replacement state recognizing means.
  • a method for starting the fuel cell system according to the third embodiment will be described below with reference to a flowchart shown in Fig. 11 .
  • the controller 43 detects the change and follows the steps of the flowchart of Fig. 11 to start the fuel cell system.
  • a detection value of the hydrogen concentration meter 51 is read and it is determined whether or not the hydrogen concentration in the hydrogen circulation pump 24 is equal to or less than a predetermined value. If it is determined that the hydrogen concentration is equal to or less than the predetermined value in S21, that is, if the result of the determination of S21 is Yes, it is determined that the fuel chamber is filled with air transmitted from the oxidizer electrode 1a during the stoppage (state B) and the process proceeds to S22.
  • the hydrogen circulation pump 24 is started to generate a negative pressure at the outlet of the fuel electrode 1b (and gas flow through the fuel electrode 1b), and then the supply of fuel gas is started. Therefore, the time period in which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b is reduced and deterioration is suppressed. Then, the process proceeds to S24, where a normal operation routine is performed.
  • State A and state C can be divided from each other on the basis of the time elapsed after the stoppage, as described in the first embodiment. Therefore, the start time may, of course, be reduced by immediately performing the normal operation routine if it is determined that the fuel chamber is in state A.
  • the predetermined value used for the determination performed in S21 is obtained in advance by experiment and is set to a hydrogen concentration at which the deterioration of the fuel electrode 1b does not progress even when the hydrogen circulation pump 24 is operated first in the fuel chamber.
  • a gap between a casing and a rotor is set to be sufficiently small so as to prevent an internal leakage from an outlet to an inlet during the operation. Therefore, the hydrogen circulation pump 24 cannot be easily filled with air compared to other portions after stopping, and is last to be filled with air in the hydrogen circulation system via diffusion.
  • Fig. 12 is a system diagram showing the structure according to the fourth embodiment.
  • the structure according to the fourth embodiment is similar to that shown in Fig. 1 except an oxygen concentration meter 52 for measuring the oxygen concentration is additionally provided at the outlet of the fuel electrode 1b of the fuel cell body 1 as an air replacement state recognizing means.
  • a method for starting the fuel cell system according to the fourth embodiment will be described below with reference to a flowchart shown in Fig. 13 .
  • the controller 43 detects the change and follows the step of the flowchart of Fig. 13 to start the fuel cell system.
  • a detection value of the oxygen concentration meter 52 is read and it is determined whether or not the oxygen concentration at the outlet of the fuel cell body 1 is equal to or less than a predetermined value. If it is determined that the oxygen concentration is equal to or less than the predetermined value in S31, that is, if the result of the determination of S31 is Yes, then it is determined that the fuel chamber is filled with hydrogen provided before the previous stoppage of power generation (state A). Accordingly, it is determined that hydrogen and oxygen are not unevenly distributed in the fuel electrode 1b and the deterioration of the fuel cell will not progress. Therefore, the process proceeds to S34, where the supply of hydrogen is started and the hydrogen circulation pump 24 is activated.
  • the order in which the supply of hydrogen is started and the hydrogen circulation pump 24 is activated is not restricted. Accordingly, the supply of hydrogen may be started and the hydrogen circulation pump 24 may be activated simultaneously. Then, the process proceeds to S33, where the normal operation routine is performed.
  • State B and state C can be divided from each other on the basis of the time elapsed after the stoppage, as described in the first embodiment. Therefore, the deterioration of the fuel cell can be suppressed by operating the hydrogen circulation pump 24 first when it is determined that the fuel chamber is in state B.
  • the predetermined value used for the determination performed in S31 is obtained in advance by experiment and is set to an oxygen concentration at which the deterioration of the fuel electrode 1b does not progress even when the normal operation routine is started in the fuel chamber immediately after the system is started.
  • the air replacement state in the fuel chamber can be detected by placing the oxygen concentration meter at the outlet of the fuel cell body 1.
  • the oxygen concentration meter may, of course, be placed at the inlet of the fuel cell body 1.
  • the outlet and the inlet of the fuel electrode 1b of the fuel cell body 1 are first to be filled with air in the hydrogen circulation system except for the inside of the fuel cell, where it is difficult to set the oxygen concentration meter.
  • Fig. 14 is a system diagram showing the structure according to the fifth embodiment.
  • the structure according to the fifth embodiment is similar to that shown in Fig. 1 except a hydrogen concentration meter 53 for measuring the hydrogen concentration is additionally provided at an outlet of the fuel electrode 1b of the fuel cell body 1 as an air replacement state recognizing means.
  • a method for starting the fuel cell system will be described below with reference to a flowchart shown in Fig. 15 .
  • the controller 43 detects the change and follows the steps of the flowchart of Fig. 15 to start the fuel cell system.
  • a detection value of the hydrogen concentration meter 53 is read and it is determined whether or not the hydrogen concentration at the outlet of the fuel cell body 1 is equal to or more than a predetermined value. If it is determined that the hydrogen concentration is equal to or more than the predetermined value in S41, that is, if the result of the determination of S41 is Yes, it is determined that the fuel chamber is filled with hydrogen provided before the previous stoppage of power generation (state A). Accordingly, it is determined that hydrogen and oxygen are not unevenly distributed in the fuel electrode 1b and the deterioration of the fuel cell does not progress. Therefore, the process proceeds to S44, where the supply of hydrogen is started and the hydrogen circulation pump 24 is activated.
  • the order in which the supply of hydrogen is started and the hydrogen circulation pump 24 is activated is not restricted. Accordingly, the supply of hydrogen may be started and the hydrogen circulation pump 24 may be activated at the same time. Then, the process proceeds to S43, where a normal operation routine is performed.
  • State B and state C can be divided from each other on the basis of the time elapsed after the stoppage, as described in the first embodiment. Therefore, the deterioration of the fuel cell can be suppressed by operating the hydrogen circulation pump 24 first when it is determined that the fuel chamber is in state B.
  • the predetermined value used for the determination performed in S41 is determined in advance by experiment and is set to a hydrogen concentration at which the deterioration of the fuel electrode 1b does not progress even when the normal operation routine is started in the fuel chamber immediately after the system is started.
  • the air replacement state in the fuel chamber can be detected by placing the hydrogen concentration meter at the outlet of the fuel cell body 1.
  • the hydrogen concentration meter may, of course, be placed at the inlet of the fuel cell body 1.
  • the outlet and the inlet of the fuel electrode 1b of the fuel cell body 1 are first to be filled with air in the hydrogen circulation system except for the inside of the fuel cell, where it is difficult to set the hydrogen concentration meter.
  • Fig. 16 is a system diagram showing the structure according to the sixth embodiment.
  • the structure according to the sixth embodiment is similar to that shown in Fig. 1 except a hydrogen-circulation-pump discharge shutoff valve 54 is additionally provided between the outlet of the hydrogen circulation pump 24 and a junction of the hydrogen supply path 22 and the hydrogen circulation path 26.
  • a method for starting the fuel cell system will be described below with reference to a flowchart shown in Fig. 17 .
  • the controller 43 detects the change and follows the steps of the flowchart of Fig. 17 to start the fuel cell system.
  • the hydrogen-circulation-pump discharge shutoff valve 54 is closed.
  • the operation of the hydrogen circulation pump 24 is started.
  • the rotational speed of the hydrogen circulation pump 24 is detected and it is determined whether or not the rotational speed is equal to or more than a predetermined value (e.g., in revolutions per second). If it is determined that the rotational speed is equal to or less than the predetermined value in S53, that is, if the result of the determination of S53 is No, then S53 is repeated until the rotational speed reaches the predetermined value.
  • a predetermined value e.g., in revolutions per second
  • the rotational speed is equal to or more than the predetermined value in S53, that is, if the result of the determination of S53 is Yes, then it is determined that a sufficient negative pressure is generated to cause sufficient gas flow through the fuel electrode 1b and the process proceeds to S54.
  • the negative pressure in the fuel electrode 1b may also be determined on the basis of pressure detected by the hydrogen pressure gage 29, instead of the rotational speed of the hydrogen circulation pump 24.
  • S54 the hydrogen-circulation-pump discharge shutoff valve 54 is opened and the process proceeds to S55.
  • S55 the supply of hydrogen is started to eliminate the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, and then the normal operation routine is performed in S56.
  • the operation of the hydrogen gas circulation pump is started after the shutoff valve 54 provided downstream of the hydrogen circulation pump is closed. Therefore, if it is determined that hydrogen provided before the previous stoppage of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur immediately after the hydrogen circulation pump 24 is activated, can be avoided and the deterioration of the fuel cell can be prevented from progressing.
  • a fuel cell system according to a seventh embodiment of the present invention will be described below.
  • the structure according to the seventh embodiment is similar to those shown in Figs. 1 and 16 except oxygen concentration meters and hydrogen concentration meters similar to the oxygen concentration meters 50 and 52 and the hydrogen concentration meter 51 and 53, respectively, are additionally provided in the hydrogen circulation pump 24 and at the outlet of the fuel cell body 1, as in the second to fourth embodiments.
  • a method for starting the fuel cell system according to the seventh embodiment will be described below with reference to a flowchart shown in Fig. 18 .
  • the controller 43 detects the change and follows the steps of the flowchart of Fig. 18 to start the fuel cell system.
  • S61 it is determined whether or not the fuel chamber is filled with hydrogen that remains after the previous stoppage of power generation. If it is determined that the fuel chamber is filled with hydrogen in S61, that is, if the result of the determination of S62 is Yes, then it is determined that the fuel chamber is filled with hydrogen that remains after the previous stoppage of power generation (state A), that hydrogen and oxygen are not unevenly distributed in the fuel electrode 1b and that the deterioration of the fuel cell will not progress. Therefore, the process proceeds to S68 and the normal operation routine is performed.
  • the process proceeds to S62, where it is determined whether or not the fuel chamber is filled with air that enters from the oxidizer electrode 1a (state B). If it is determined that the fuel chamber is filled with air in S62, that is, if the result of the determination of S62 is Yes, the uneven distribution of hydrogen and oxygen will not occur in the fuel electrode 1b even in the case where the hydrogen-circulation-pump discharge shutoff valve 54 is not closed. Therefore, the routine for closing the hydrogen-circulation-pump discharge shutoff valve 54 (S63) is skipped and the routine for operating the hydrogen circulation pump 24 is performed in S64.
  • the air replacement state in the fuel chamber is estimated on the basis of the time elapsed after the stoppage and the detection results of the oxygen concentration meters 50 and 52 and the hydrogen concentration meters 51 and 53 disposed in the hydrogen circulation pump 24 and at the outlet of the fuel cell body 1, similar to the first, second, third, fourth, and fifth embodiments.
  • the effects of the second to seventh embodiments may also be obtained when the fuel electrode and the air electrode are stopped in inert gas (the case in the fuel chamber is not completely filled with the inert gas and hydrogen remains in the fuel chamber).

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Abstract

A fuel cell system includes a controller that estimates or detects an air replacement state of a fuel electrode and a hydrogen circulation path while the operation of the fuel cell system is stopped. Upon starting the fuel cell system, the controller changes the order in which the operation of a hydrogen circulation pump is started and a hydrogen pressure regulator is opened to start the supply of hydrogen gas on the basis of the estimated or detected air replacement state, thereby preventing deterioration caused by uneven distribution of air and hydrogen in the fuel electrode.

Description

    Technical Field
  • The present invention relates to a proton exchange membrane fuel cell system and a method for starting up a fuel cell system.
    • Background Art
  • In general, if hydrogen and oxygen are unevenly distributed in a fuel electrode of a fuel cell when the fuel cell is started, a local potential is generated in a region where a hydrogen concentration is relatively high and serves to cause a current flow in a direction opposite to that in a normal power-generating state in a region where an oxygen concentration is relatively high. Therefore, an oxidizer electrode, in particular, quickly deteriorates. In order to solve this problem, an invention for discharging oxygen that remains in the fuel electrode and replacing the oxygen with hydrogen gas in a short time is disclosed in, for example, Japanese Unexamined Patent Application Publication No. 2004-139984 (see page 12 and Fig. 14). According to this invention, when a fuel cell is started, a control value of a secondary pressure regulator is set to be higher than a supply pressure in a normal power-generating state and hydrogen is supplied to the fuel cell by opening a hydrogen supply solenoid valve while driving a hydrogen pump.
    • Disclosure of Invention
  • However, according to the start method disclosed in the above-mentioned publication in which the hydrogen pump is started first, even when the fuel electrode of the fuel cell is filled with air (or hydrogen), if the gas composition in the fuel electrode and a hydrogen circulation path is uneven, hydrogen (or air) that remains in the hydrogen circulation path flows into the fuel electrode immediately after the operation of the hydrogen pump is started. In addition, it requires a relatively long time for the hydrogen circulation pump to accelerate to a predetermined rotational speed after the hydrogen circulation pump is started. Therefore, it takes a relatively long time to eliminate the uneven distribution of hydrogen and oxygen in the fuel electrode, and accordingly the deterioration of the fuel cell progresses.
  • In order to solve the above-described problem, a fuel cell system according to one aspect of the present invention includes an air-replacement-state recognizing unit including at least one of a timer, oxygen concentration sensor and a fuel-gas concentration sensor being disposed at a portion, where replacement by air is finished first or last in the fuel electrode, for estimating or detecting a state in which hydrogen and air are unevenly distributed in at least one of a fuel electrode and a fuel-gas circulation path and a start control device for operating the fuel-gas circulation pump after supplying the fuel gas upon starting the fuel cell if the air-replacement-state recognizing unit estimates or detects that hydrogen and air are unevenly distributed.
  • According to the present invention, the timings of activation of the fuel-gas circulation pump and the supply of fuel gas are changed on the basis of the air replacement state and, as a result, deterioration of the fuel cell caused by uneven distribution of the fuel gas and air in the fuel electrode caused by air infiltration into the fuel chamber (the fuel electrode, the fuel-gas circulation path, and fuel-gas circulating means) is prevented.
    • Brief Description of the Drawings
    • Fig. 1 is a diagram illustrating a fuel cell system.
    • Fig. 2 is a diagram illustrating a single cell in a fuel cell.
    • Fig. 3 is a diagram illustrating an inner state (state A) of a fuel chamber.
    • Fig. 4 is a diagram illustrating another inner state (state B) of the fuel chamber.
    • Fig. 5 is a diagram illustrating another inner state (state C) of the fuel chamber.
    • Fig. 6 is a flowchart of a process performed in a fuel cell system according to a first embodiment of the present invention.
    • Fig. 7 is a diagram illustrating the fuel cell system according to the first embodiment of the present invention.
    • Fig. 8 is a diagram illustrating a fuel cell system according to a second embodiment of the present invention.
    • Fig. 9 is a flowchart of a process performed in the fuel cell system according to the second embodiment of the present invention.
    • Fig. 10 is a diagram illustrating a fuel cell system according to a third embodiment of the present invention.
    • Fig. 11 is a flowchart of a process performed in the fuel cell system according to the third embodiment of the present invention.
    • Fig. 12 is a diagram illustrating a fuel cell system according to a fourth embodiment of the present invention.
    • Fig. 13 is a flowchart of a process performed in the fuel cell system according to the fourth embodiment of the present invention.
    • Fig. 14 is a diagram illustrating a fuel cell system according to a fifth embodiment of the present invention.
    • Fig. 15 is a flowchart of a process performed in the fuel cell system according to the fifth embodiment of the present invention.
    • Fig. 16 is a diagram illustrating a fuel cell system according to a sixth embodiment of the present invention.
    • Fig. 17 is a flowchart of a process performed in the fuel cell system according to the sixth embodiment of the present invention.
    • Fig. 18 is a flowchart of a process performed in a fuel cell system according to a seventh embodiment of the present invention.
    Reference Numerals
    • 1
    fuel cell body
    1a
    oxidizer electrode
    1b
    fuel electrode
    11
    air compressor
    12
    air supply path
    13
    air-system humidifier
    14
    air discharge path
    15
    air pressure regulator
    16
    air pressure gage
    17
    hydrogen detector
    21
    high-pressure hydrogen tank
    22
    hydrogen supply path
    23
    hydrogen pressure regulator
    24
    hydrogen circulation pump
    25
    hydrogen-system humidifier
    26
    hydrogen circulation path
    27
    hydrogen discharge path
    28
    hydrogen discharge valve
    29
    hydrogen pressure gage
    31
    cooling water pump
    32
    cooling water circulation path
    33
    heat exchanger
    34
    cooling water thermometer
    40
    load device
    41
    voltmeter
    42
    ammeter
    43
    controller
    50
    oxygen concentration meter
    51
    hydrogen concentration meter
    52
    oxygen concentration meter
    53
    hydrogen concentration meter
    54
    hydrogen-circulation-pump discharge shutoff valve
    60
    timer
    Detailed Description
  • Next, embodiments of the present invention will be described in detail with reference to the drawings.
  • First, the overall structure of a fuel cell system to which the present invention may be applied will be described below with reference to Fig. 1, which is a diagram illustrating the fuel cell system and Fig. 2, which is a diagram illustrating a single cell in a fuel cell.
    • Fuel Cell Body
  • As shown in Fig. 2, a single cell 100 of a fuel cell includes a membrane-electrode assembly (MEA) 101 including a solid polymer electrolyte membrane 102, a fuel-electrode catalyst layer 103 provided on one side of the electrolyte membrane 102, and an oxidizer-electrode catalyst layer 104 provided on the other side of the electrolyte membrane 102; a fuel-gas diffusion layer 105 provided on one side of the MEA 101; an oxidizing-gas diffusion layer 106 provided on the other side of the MEA 101; and separators 107 and 108.
  • A fuel-gas path 109 is provided between the separator 107 and the fuel-gas diffusion layer 105 and an oxidizing-gas path 110 is provided between the separator 108 and the oxidizing-gas diffusion layer 106. The fuel cell body includes a plurality of cells similar to the single cell 100. Fuel gas (hydrogen) and oxidizing gas (air) are externally supplied to the fuel cell body and are caused to flow through the fuel-gas path 109 and the oxidizing-gas path 110, respectively, so that electric power is generated as a result of electrochemical reaction.
  • A fuel cell system to which the present invention may be applied includes a fuel cell body 1, an air system for supplying air, a hydrogen system for supplying hydrogen, a cooling water system for supplying cooling water, and a load system for extracting the electric power from the fuel cell body 1.
    • Air System
  • The air system includes an air compressor 11 for sucking in and compressing air, an air-system humidifier 13 for humidifying the air compressed by the air compressor 11 and supplying the humidified air to an oxidizer electrode 1a, an air pressure gage 16 for detecting the pressure of the air supplied to the oxidizer electrode 1a, and an air pressure regulator 15 for adjusting the pressure in the oxidizer electrode 1a by regulating the air discharged from the oxidizer electrode 1a.
  • The air compressed by the air compressor 11 is supplied through the air supply path 12 to the air-system humidifier 13, and is humidified. Then, the humidified air is supplied to the oxidizer electrode 1a of the fuel cell body 1, and is consumed by the electrochemical reaction in the fuel cell body 1. Then, the exhaust air is caused to flow through the air discharge path 14 and is discharged from the system after the pressure adjustment is performed by the air pressure regulator 15. The pressure of the air supplied to the oxidizer electrode 1a is detected by the air pressure gage 16 disposed at an inlet of the oxidizer electrode 1a, and the air pressure regulator 15 is controlled such that the detected pressure becomes equal to a desired pressure. The air-system humidifier 13 may include a water vapor exchange membrane for utilizing moisture included in the exhaust or may use pure water that is externally supplied.
  • A hydrogen detector 17 for detecting hydrogen included in the exhaust air is disposed downstream of the air pressure regulator 15. Accordingly, hydrogen that enters through the electrolyte membrane 102 from the fuel electrode to the oxidizer electrode and hydrogen that leaks from a sealed portion can be detected.
    • Hydrogen System
  • The hydrogen system includes a high-pressure hydrogen tank 21 that stores hydrogen gas, a hydrogen pressure regulator 23 for adjusting the pressure of the hydrogen, a hydrogen-system humidifier 25 for humidifying the hydrogen after the pressure thereof is adjusted and supplying the humidified hydrogen to a fuel electrode 1b, a hydrogen pressure gage 29 for detecting the pressure of the hydrogen supplied to the fuel electrode 1b, a hydrogen circulation pump 24 and a hydrogen circulation path 26 for circulating the hydrogen discharged from an outlet of the fuel electrode 1b to an inlet of the fuel electrode 1b, and a hydrogen discharge path 27 and a hydrogen discharge valve 28 for discharging impurities accumulated in the fuel electrode 1b and the hydrogen circulation path 26 from the system.
  • The hydrogen supplied from the high-pressure hydrogen tank 21 flows through the hydrogen supply path 22 via the hydrogen pressure regulator 23, where the pressure of the hydrogen is adjusted to a desire pressure, and joins the discharge hydrogen circulated by the hydrogen circulation pump 24. Then, the hydrogen is humidified by the hydrogen-system humidifier 25, and is fed to the fuel electrode 1b of the fuel cell body 1. The pressure of the hydrogen supplied to the fuel electrode 1b is detected by the hydrogen pressure gage 29 provided at the inlet of the fuel electrode 1b, and the hydrogen pressure regulator 23 is controlled such that the detected pressure becomes equal to the desired pressure. After the hydrogen is consumed by the electrochemical reaction in the fuel cell body 1, the excess hydrogen is caused to pass through the hydrogen circulation path 26 by the hydrogen circulation pump 24 and is used for power generation again.
  • On the other hand, nitrogen that enters from the oxidizer electrode 1a to the fuel electrode 1b during the operation and impurities included in the high-pressure hydrogen tank 21 accumulate in the hydrogen system. Therefore, these impurities are discharged from the system through the hydrogen discharge path 27 by opening the hydrogen discharge valve 28.
    • Cooling Water System
  • The cooling water system is provided to maintain the temperature of the fuel cell body 1 at an adequate temperature by removing heat generated as a result of power generation performed by the fuel cell body 1. The cooling water system includes a cooling water pump 31 for circulating the cooling water, a cooling water circulation path 32, a heat exchanger 33 for dissipating heat to the outside of the system, and a cooling water thermometer 34 for detecting the temperature of the cooling water at a position near a cooling-water outlet of the fuel cell body 1.
  • The cooling water is pressurized by the cooling water pump 31 so as to flow through the fuel cell body 1, and thereby absorbs heat. Then, the cooling water flows through the cooling water circulation path 32 to the heat exchanger 33, where the heat is discharged to the outside of the system. Then, the cooling water is caused to flow through the fuel cell body 1 again by the cooling water pump 31. The temperature of the cooling water is monitored by the cooling water thermometer 34 and is adjusted to a temperature appropriate for the power generation level provided by the fuel cell body by controlling the amount of air flow supplied to the heat exchanger 33 by a blower.
    • Load System
  • A load device 40 that absorbs the electric power generated by the fuel cell body 1 functions as, for example, an inverter for supplying electric power to a vehicle drive motor in a fuel cell vehicle. A power generation voltage of the fuel cell body 1 is detected by a voltmeter 41 and a current supplied to the load device 40 from the fuel cell body 1 is detected by an ammeter 42.
    • Control System
  • A controller 43 operates as a start control device to control the overall operation of the fuel cell system including the fuel cell body 1. The controller 43 includes, for example, a central processing unit (CPU), a read only memory (ROM) that stores control programs and control parameters, a working random access memory (RAM), and a microprocessor including an input/output interface.
  • The controller 43 outputs control signals to the air compressor 11, the air pressure regulator 15, the hydrogen pressure regulator 23, the hydrogen discharge valve 28, the cooling water pump 31, and the load device 40 on the basis of detected signals obtained from the air pressure gage 16, the hydrogen pressure gage 29, the cooling water thermometer 34, the voltmeter 41, and the ammeter 42 in order to adjust the pressure, temperature, the amount of flow, and the load in the fuel cell body 1.
  • Next, the state of the fuel chamber (the hydrogen supply path 22, the hydrogen circulation pump 24, the hydrogen-system humidifier 25, the fuel electrode 1b, and the hydrogen circulation path 26 that varies in a period from when the fuel cell system stops to when the fuel cell system is restarted will be described with reference to Figs. 3, 4, and 5. In the figures, the hydrogen-system humidifier 25 is omitted.
    • A. Immediately after stoppage
  • In a period immediately after the stoppage, the fuel chamber is filled with hydrogen provided before the power generation was stopped.
    • B. After an extended time from stoppage (or when air replacement occurs)
  • After a sufficient time from the stoppage, air leaks or otherwise enters through the MEA 101 from the oxidizer electrode 1a to the fuel electrode 1b and diffuses into the fuel chamber so that the fuel chamber becomes filled with the air. The amount of the original hydrogen that has been replaced by the infiltrated air is referred to herein as the air replacement state. The time required for the air to fill the fuel chamber varies in accordance with the material, the thickness, the temperature, etc., of the MEA, but is generally about several hours.
    • C. Several minutes to several tens of minutes after stoppage
  • In a relatively short time period after the stoppage, the air diffuses into the fuel electrode 1b, whereas other portions (the hydrogen circulation pump 24, the hydrogen-system humidifier 25, and the hydrogen circulation path 26) remain filled with hydrogen provided in the previous operation of power generation. Therefore, different from state B, the air and hydrogen are unevenly distributed in the fuel chamber. The time period and rate in which the hydrogen is replaced with air varies in accordance with the material, the thickness, the temperature, etc., of the MEA, but is generally about several minutes to several tens of minutes. Here, the uneven distribution refers to the state in which hydrogen and oxygen (or gases having different hydrogen densities) exist separately within the fuel chamber.
    • First Embodiment
  • Next, a fuel cell system according to a first embodiment of the present invention will be described below. The structure of the fuel cell system according to the first embodiment is similar to that shown in Fig. 1. However, the controller 43 includes an air-replacement-state estimator for estimating an air replacement state of the fuel electrode 1b and the hydrogen circulation path 26 when the fuel cell system is stopped. When the fuel cell system is started, the controller 43 controls the timings at which the operation of the hydrogen circulation pump 24 is started and the hydrogen pressure regulator 23 is opened to start supplying the fuel gas on the basis of the estimated air replacement state.
    • Start Method for First Embodiment
  • Next, a method for starting the fuel cell system according to the present embodiment will be described below with reference to a flowchart shown in Fig. 6. When, for example, the state of a key switch is changed from Off to On, the controller 43 detects the change and follows the steps of the flowchart of Fig. 6 to start the fuel cell system.
  • First, in Step 01 ('Step' is hereafter abbreviated as 'S'), it is determined whether or not a time elapsed after the previous stoppage is within a first predetermined time by referring to an air replacement state recognizing means (e.g., a timer 60).
  • If it is determined that the elapsed time is equal to or less than the first predetermined time in S01, that is, if the result of the determination of S01 is Yes, it is determined that the fuel chamber is filled with hydrogen provided in the previous operation of power generation (state A). Accordingly, it is determined that hydrogen and oxygen are not unevenly distributed in the fuel electrode 1b and the deterioration will not progress during start up. Therefore, the process proceeds to S06, where the supply of hydrogen is started and the hydrogen circulation pump 24 is activated. Here, the order in which the supply of hydrogen is started and the hydrogen circulation pump 24 is activated is not restricted. Accordingly, the supply of hydrogen may be started and the hydrogen circulation pump 24 may be activated at the same time. Then, the process proceeds to S05, where a normal operation routine is performed. The normal operation routine is a control routine for performing a normal operation. More specifically, in the normal operation, the air system, the hydrogen system, the cooling system, the load system, and the control system are operated in accordance with the load requirement of the system. Here, the uneven distribution refers to the state in which hydrogen and oxygen (or gases having different hydrogen densities) exist separately.
  • If it is determined that the elapsed time is more than the first predetermined time in S01, that is, if the result of the determination of S01 is No, the process proceeds to S02, where it is determined whether or not the time elapsed after the previous stoppage is equal to or more than a second predetermined time by referring to the timer.
  • If it is determined that the elapsed time is equal to or more than the second predetermined time in S02, that is, if the result of the determination of S02 is Yes, it is determined that the fuel chamber is filled with air from the oxidizer electrode 1a during the stoppage (state B) and the process proceeds to S03. In S03, first, the hydrogen circulation pump 24 is activated to generate a negative pressure at the outlet of (and gas flow through) the fuel electrode 1b, and then the supply of hydrogen gas is started by executing a hydrogen supply start routine. Therefore, the time period in which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b is reduced and the deterioration is reduced. Then, the process proceeds to S05, where the normal operation routine is performed.
  • If it is determined that the elapsed time is less than the second predetermined time in S02, that is, if the result of the determination of S02 is No, it is determined that hydrogen that remains after the previous stoppage of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), and the process proceeds to S04. In S04, first, the supply of hydrogen gas is started, and then the hydrogen circulation pump 24 is started. Therefore, the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur under prior art methods immediately after the hydrogen circulation pump is activated, can be avoided and the deterioration can be prevented from progressing. The process then proceeds to S05, where the normal operation routine is performed.
  • The above-described embodiment provides the following effects:
    1. (1) If it is determined that the fuel electrode 1b is filled with hydrogen (state A), then the normal power generating operation can be started immediately. Therefore, the start time can be reduced.
    2. (2) If it is determined that fuel electrode 1b is substantially filled with air (state B), then high-pressure hydrogen can be supplied and drawn through the fuel electrode 1b in response to a negative pressure generated in the fuel electrode 1b by the hydrogen circulation pump 24. Therefore, the time period during which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b can be reduced and the deterioration of the fuel cell can be suppressed.
    3. (3) If it is determined that hydrogen that remains after the previous stoppage of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), then the hydrogen circulation pump 24 is started after the supply of hydrogen gas is started. Therefore, the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur using prior art methods immediately after the hydrogen circulation pump is operated, can be avoided and the deterioration of the fuel cell can be prevented from progressing.
    Estimation of the air replacement state of the fuel chamber based on the stop period and correction based on temperature
  • Next, the first and second predetermined times for determining the mixed air state of the fuel chamber on the basis of the time elapsed after the previous stoppage until the restart will be described below. To determine these times, an oxygen concentration sensor or a hydrogen concentration sensor is disposed at a certain position in the fuel chamber of an experimental fuel cell system and a variation with time in the concentration of oxygen or hydrogen after the fuel cell system is stopped is experimentally measured. Then, the first predetermined time is determined as a time period during which the oxygen concentration is equal to or less than a predetermined value (the hydrogen concentration is equal to or more than a predetermined value) and at which the deterioration does not progress even when the normal operation routine is started in the fuel chamber immediately after the fuel cell system is started.
  • The second predetermined time is based upon temperature and is determined as a time period required for the oxygen concentration to become equal to or more than a predetermined value (for the hydrogen concentration to become equal to or less than a predetermined value) at which the deterioration of the fuel electrode 1b does not progress even when the hydrogen circulation pump 24 is operated first in the fuel chamber.
  • The time rate at which the air enters from the oxidizer electrode 1a to the fuel electrode 1b depends on the temperature of the fuel cell body 1, and the transmission speed is increased as the temperature is increased. Therefore, an experiment of, for example, varying the fuel cell temperature detected by the cooling water thermometer 34 and measuring the variation with time in gas concentration in the fuel chamber is performed and a correction value (correction coefficient) shown in Fig. 7 is determined and stored in the controller in advance. The first and second predetermined times are multiplied by the correction value so that first and second predetermined times can be used as more accurate determination thresholds.
    • Second Embodiment
  • A fuel cell system according to a second illustrated embodiment of the present invention will be described below. Fig. 8 is a system diagram showing the structure according to the second embodiment. The structure according to the second embodiment is similar to that shown in Fig. 1 except an oxygen concentration meter 50 for measuring the oxygen concentration in the hydrogen circulation pump 24 is additionally provided as an air replacement state recognizing means.
    • Start Method
  • A method for starting the fuel cell system according to the second embodiment will be described below with reference to a flowchart shown in Fig. 9. When, for example, the state of a key switch is changed from Off to On, the controller 43 detects the change and follows the steps of the flowchart of Fig. 9 to start the fuel cell system.
  • First, in S11, a detection value of the oxygen concentration meter 50 is read and it is determined whether or not the oxygen concentration in the hydrogen circulation pump 24 is equal to or more than a predetermined value. If it is determined that the oxygen concentration is equal to or more than the predetermined value in S11, that is, if the result of the determination of S11 is Yes, it is determined that the fuel chamber is filled with air transmitted from the oxidizer electrode 1a during the stoppage (state B) and the process proceeds to S12. In S12, first, the hydrogen circulation pump 24 is started to generate a negative pressure at the outlet of (and gas flow through) the fuel electrode 1b, and then the supply of fuel gas is started. Therefore, the time period in which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b is reduced and the deterioration is suppressed. The process then proceeds to S14, where the normal operation routine is performed.
  • If is determined that the oxygen concentration is less than the predetermined value in S11, that is, if the result of the determination of S11 is No, it is determined that hydrogen that remains after the previous stoppage of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C) or that the fuel chamber is filled with hydrogen provided before the previous stoppage of power generation (state A), and the process proceeds to S13.
  • In S13, first, the supply of hydrogen gas is started, and then the operation of the hydrogen circulation pump 24 is started. Therefore, the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur under prior methods immediately after the hydrogen circulation pump is started, can be avoided and the deterioration of the fuel cell can be prevented from progressing. Then, the process proceeds to S14, where the normal operation routine is performed.
  • The above-described embodiment provides the following effects:
    1. (1) If it is determined that fuel electrode 1b is filled with air (state B), high-pressure hydrogen can be supplied after a negative pressure is generated in, and gas flow resumes, through the fuel electrode 1b by operation of the hydrogen circulation pump 24. Therefore, the time period during which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b can be reduced and the deterioration of the fuel cell can be suppressed.
    2. (2) If it is determined that hydrogen provided in the previous operation of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C) or that the fuel chamber 1b is filled with hydrogen (state A), the operation of the hydrogen circulation pump 24 is started after the supply of hydrogen gas is started. Therefore, the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur using prior methods immediately after the hydrogen circulation pump is operated, can be avoided and the deterioration of the fuel cell can be prevented from progressing.
  • State A and state C can be divided from each other on the basis of the time elapsed after the stoppage, as described in the first embodiment. Therefore, the start time may, of course, be reduced by immediately performing the normal operation routine if it is determined that the fuel chamber is in state A.
    • Predetermined value of oxygen concentration
  • The predetermined value used for the determination performed in S11 is obtained in advance by experiment and is set to an oxygen concentration at which the deterioration of the fuel electrode 1b does not progress even when the hydrogen circulation pump 24 is operated first in the fuel chamber.
    • Reason why the oxygen concentration meter is disposed in the hydrogen circulation pump 24
  • In the hydrogen circulation pump 24, a gap between a casing and a rotor is set to be sufficiently small so as to prevent an internal leakage from an outlet to an inlet during operation. Therefore, the hydrogen circulation pump 24 cannot be easily filled with air compared to other portions after stopping, and is last to be filled with air in the hydrogen circulation system via diffusion.
    • Third Embodiment
  • A fuel cell system according to a third illustrated embodiment of the present invention will be described below. Fig. 10 is a system diagram showing the structure according to the third embodiment. The structure according to the third embodiment is similar to that shown in Fig. 1 except a hydrogen concentration meter 51 for measuring the hydrogen concentration in the hydrogen circulation pump 24 is additionally provided as an air replacement state recognizing means.
    • Start Method
  • A method for starting the fuel cell system according to the third embodiment will be described below with reference to a flowchart shown in Fig. 11. When, for example, the state of a key switch is changed from Off to On, the controller 43 detects the change and follows the steps of the flowchart of Fig. 11 to start the fuel cell system.
  • First, in S21, a detection value of the hydrogen concentration meter 51 is read and it is determined whether or not the hydrogen concentration in the hydrogen circulation pump 24 is equal to or less than a predetermined value. If it is determined that the hydrogen concentration is equal to or less than the predetermined value in S21, that is, if the result of the determination of S21 is Yes, it is determined that the fuel chamber is filled with air transmitted from the oxidizer electrode 1a during the stoppage (state B) and the process proceeds to S22. In S22, first, the hydrogen circulation pump 24 is started to generate a negative pressure at the outlet of the fuel electrode 1b (and gas flow through the fuel electrode 1b), and then the supply of fuel gas is started. Therefore, the time period in which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b is reduced and deterioration is suppressed. Then, the process proceeds to S24, where a normal operation routine is performed.
  • If is determined that the hydrogen concentration is more than the predetermined value in S21, that is, if the result of the determination of S21 is No, it is determined that hydrogen that remains after the previous stoppage of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C) or that the fuel chamber is filled with hydrogen provided before the previous stoppage of power generation (state A), and the process proceeds to S23.
  • In S23, first, the supply of hydrogen gas is started, and then the hydrogen circulation pump 24 is started. Therefore, the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur using prior art methods immediately after the hydrogen circulation pump is operated, can be avoided and the deterioration of the fuel cell is prevented from progressing. Then, the process proceeds to S24, where the normal operation routine is performed.
  • The above-described embodiment provides the following effects:
    1. (1) If it is determined that fuel electrode 1b is filled with air (state B), high-pressure hydrogen is supplied after a negative pressure is generated in the fuel electrode 1b (and gas flow resumes through the fuel electrode 1b) by operation of the hydrogen circulation pump 24. Therefore, the time period during which hydrogen and oxygen are unevenly distributed in the fuel electrode 1b is reduced and the deterioration of the fuel cell is suppressed.
    2. (2) If it is determined that hydrogen provided in the previous operation of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C) or that the fuel chamber 1b is filled with hydrogen (state A), the operation of the hydrogen circulation pump 24 is started after the supply of hydrogen gas is started. Therefore, the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur using prior art methods immediately after the hydrogen circulation pump is operated, is avoided and the deterioration of the fuel cell is prevented from progressing.
  • State A and state C can be divided from each other on the basis of the time elapsed after the stoppage, as described in the first embodiment. Therefore, the start time may, of course, be reduced by immediately performing the normal operation routine if it is determined that the fuel chamber is in state A.
    • Predetermined value of hydrogen concentration
  • The predetermined value used for the determination performed in S21 is obtained in advance by experiment and is set to a hydrogen concentration at which the deterioration of the fuel electrode 1b does not progress even when the hydrogen circulation pump 24 is operated first in the fuel chamber.
    • Reason why the hydrogen concentration meter is disposed in the hydrogen circulation pump 24
  • In the hydrogen circulation pump 24, a gap between a casing and a rotor is set to be sufficiently small so as to prevent an internal leakage from an outlet to an inlet during the operation. Therefore, the hydrogen circulation pump 24 cannot be easily filled with air compared to other portions after stopping, and is last to be filled with air in the hydrogen circulation system via diffusion.
    • Fourth Embodiment
  • Next, a fuel cell system according to a fourth illustrated embodiment of the present invention will be described below. Fig. 12 is a system diagram showing the structure according to the fourth embodiment. The structure according to the fourth embodiment is similar to that shown in Fig. 1 except an oxygen concentration meter 52 for measuring the oxygen concentration is additionally provided at the outlet of the fuel electrode 1b of the fuel cell body 1 as an air replacement state recognizing means.
    • Start Method
  • A method for starting the fuel cell system according to the fourth embodiment will be described below with reference to a flowchart shown in Fig. 13. When, for example, the state of a key switch is changed from Off to On, the controller 43 detects the change and follows the step of the flowchart of Fig. 13 to start the fuel cell system.
  • First, in S31, a detection value of the oxygen concentration meter 52 is read and it is determined whether or not the oxygen concentration at the outlet of the fuel cell body 1 is equal to or less than a predetermined value. If it is determined that the oxygen concentration is equal to or less than the predetermined value in S31, that is, if the result of the determination of S31 is Yes, then it is determined that the fuel chamber is filled with hydrogen provided before the previous stoppage of power generation (state A). Accordingly, it is determined that hydrogen and oxygen are not unevenly distributed in the fuel electrode 1b and the deterioration of the fuel cell will not progress. Therefore, the process proceeds to S34, where the supply of hydrogen is started and the hydrogen circulation pump 24 is activated. Here, the order in which the supply of hydrogen is started and the hydrogen circulation pump 24 is activated is not restricted. Accordingly, the supply of hydrogen may be started and the hydrogen circulation pump 24 may be activated simultaneously. Then, the process proceeds to S33, where the normal operation routine is performed.
  • If it is determined that the oxygen concentration is more than the first predetermined time in S31, that is, if the result of the determination at S31 is No, it is determined that the fuel chamber is filled with air transmitted from the oxidizer electrode 1a during the stoppage (state B) or that hydrogen provided before the previous stoppage of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), and the process proceeds to S32. In S32, first, the supply of hydrogen gas is started, and then hydrogen circulation pump 24 is started. Therefore, uneven distribution of hydrogen and oxygen can be avoided and the deterioration of the fuel cell can be prevented from progressing. Then, the process proceeds to S33, where the normal operation routine is performed.
  • The above-described embodiment provides the following effects:
    1. (1) If it is determined that the fuel electrode 1b is filled with hydrogen (state A), the normal power generating operation can be started immediately. Therefore, the start time can be reduced.
    2. (2) If it is determined that the fuel chamber is filled with air transmitted from the oxidizer electrode 1a during the stoppage (state B) or that hydrogen provided in the previous operation of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), the operation of the hydrogen circulation pump 24 is started after the supply of hydrogen gas is started. Therefore, the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur using prior art methods immediately after the hydrogen circulation pump is operated, can be avoided and the deterioration of the fuel cell can be prevented from progressing.
  • State B and state C can be divided from each other on the basis of the time elapsed after the stoppage, as described in the first embodiment. Therefore, the deterioration of the fuel cell can be suppressed by operating the hydrogen circulation pump 24 first when it is determined that the fuel chamber is in state B.
    • Predetermined value of oxygen concentration
  • The predetermined value used for the determination performed in S31 is obtained in advance by experiment and is set to an oxygen concentration at which the deterioration of the fuel electrode 1b does not progress even when the normal operation routine is started in the fuel chamber immediately after the system is started.
    • Reason why the oxygen concentration meter is disposed at the outlet of the fuel cell body 1
  • Since the air enters from the oxidizer electrode 1a into the fuel electrode 1b during the stoppage, the air replacement state in the fuel chamber can be detected by placing the oxygen concentration meter at the outlet of the fuel cell body 1. The oxygen concentration meter may, of course, be placed at the inlet of the fuel cell body 1. The outlet and the inlet of the fuel electrode 1b of the fuel cell body 1 are first to be filled with air in the hydrogen circulation system except for the inside of the fuel cell, where it is difficult to set the oxygen concentration meter.
    • Fifth Embodiment
  • Next, a fuel cell system according to a fifth illustrated embodiment of the present invention will be described below. Fig. 14 is a system diagram showing the structure according to the fifth embodiment. The structure according to the fifth embodiment is similar to that shown in Fig. 1 except a hydrogen concentration meter 53 for measuring the hydrogen concentration is additionally provided at an outlet of the fuel electrode 1b of the fuel cell body 1 as an air replacement state recognizing means.
    • Start Method
  • Next, a method for starting the fuel cell system according to the present embodiment will be described below with reference to a flowchart shown in Fig. 15. When, for example, the state of a key switch is changed from Off to On, the controller 43 detects the change and follows the steps of the flowchart of Fig. 15 to start the fuel cell system.
  • First, in S41, a detection value of the hydrogen concentration meter 53 is read and it is determined whether or not the hydrogen concentration at the outlet of the fuel cell body 1 is equal to or more than a predetermined value. If it is determined that the hydrogen concentration is equal to or more than the predetermined value in S41, that is, if the result of the determination of S41 is Yes, it is determined that the fuel chamber is filled with hydrogen provided before the previous stoppage of power generation (state A). Accordingly, it is determined that hydrogen and oxygen are not unevenly distributed in the fuel electrode 1b and the deterioration of the fuel cell does not progress. Therefore, the process proceeds to S44, where the supply of hydrogen is started and the hydrogen circulation pump 24 is activated. Here, the order in which the supply of hydrogen is started and the hydrogen circulation pump 24 is activated is not restricted. Accordingly, the supply of hydrogen may be started and the hydrogen circulation pump 24 may be activated at the same time. Then, the process proceeds to S43, where a normal operation routine is performed.
  • If it is determined that the hydrogen concentration is less than the first predetermined time in S41, that is, if the result of the determination of S41 is No, then it is determined that the fuel chamber is filled with air that enters from the oxidizer electrode 1a during the stoppage (state B) or that hydrogen provided before the previous stoppage of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), and the process proceeds to S42.
  • In S42, first, the supply of hydrogen gas is started, and then the operation of the hydrogen circulation pump 24 is started. Therefore, uneven distribution of hydrogen and oxygen can be avoided and the deterioration of the fuel cell can be prevented from progressing. Then, the process proceeds to S43, where the normal operation routine is performed.
  • The above-described embodiment provides the following effects:
    1. (1) If it is determined that the fuel electrode 1b is filled with hydrogen (state A), the normal power generating operation can be started immediately. Therefore, the start time can be reduced.
    2. (2) If it is determined that the fuel chamber is filled with air transmitted from the oxidizer electrode 1a during the stoppage (state B) or that hydrogen provided in the previous operation of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), the hydrogen circulation pump 24 is started after the supply of hydrogen gas is started. Therefore, the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur using prior art methods immediately after the hydrogen circulation pump is operated, can be avoided and the deterioration of the fuel cell can be prevented from progressing.
  • State B and state C can be divided from each other on the basis of the time elapsed after the stoppage, as described in the first embodiment. Therefore, the deterioration of the fuel cell can be suppressed by operating the hydrogen circulation pump 24 first when it is determined that the fuel chamber is in state B.
    • Predetermined value of hydrogen concentration
  • The predetermined value used for the determination performed in S41 is determined in advance by experiment and is set to a hydrogen concentration at which the deterioration of the fuel electrode 1b does not progress even when the normal operation routine is started in the fuel chamber immediately after the system is started.
    • Reason why hydrogen concentration meter is disposed at the outlet of the fuel cell body 1
  • Since the air enters from the oxidizer electrode 1a to the fuel electrode 1b during the stoppage, the air replacement state in the fuel chamber can be detected by placing the hydrogen concentration meter at the outlet of the fuel cell body 1. The hydrogen concentration meter may, of course, be placed at the inlet of the fuel cell body 1. The outlet and the inlet of the fuel electrode 1b of the fuel cell body 1 are first to be filled with air in the hydrogen circulation system except for the inside of the fuel cell, where it is difficult to set the hydrogen concentration meter.
    • Sixth Embodiment
  • A fuel cell system according to a sixth illustrated embodiment of the present invention will be described below. Fig. 16 is a system diagram showing the structure according to the sixth embodiment. The structure according to the sixth embodiment is similar to that shown in Fig. 1 except a hydrogen-circulation-pump discharge shutoff valve 54 is additionally provided between the outlet of the hydrogen circulation pump 24 and a junction of the hydrogen supply path 22 and the hydrogen circulation path 26.
    • Start Method
  • Next, a method for starting the fuel cell system according to the present embodiment will be described below with reference to a flowchart shown in Fig. 17. When, for example, the state of a key switch is changed from Off to On, the controller 43 detects the change and follows the steps of the flowchart of Fig. 17 to start the fuel cell system.
  • First, in S51, the hydrogen-circulation-pump discharge shutoff valve 54 is closed. Then, in S52, the operation of the hydrogen circulation pump 24 is started. Then, in S53, the rotational speed of the hydrogen circulation pump 24 is detected and it is determined whether or not the rotational speed is equal to or more than a predetermined value (e.g., in revolutions per second). If it is determined that the rotational speed is equal to or less than the predetermined value in S53, that is, if the result of the determination of S53 is No, then S53 is repeated until the rotational speed reaches the predetermined value.
  • If it is determined that the rotational speed is equal to or more than the predetermined value in S53, that is, if the result of the determination of S53 is Yes, then it is determined that a sufficient negative pressure is generated to cause sufficient gas flow through the fuel electrode 1b and the process proceeds to S54. The negative pressure in the fuel electrode 1b may also be determined on the basis of pressure detected by the hydrogen pressure gage 29, instead of the rotational speed of the hydrogen circulation pump 24.
  • In S54, the hydrogen-circulation-pump discharge shutoff valve 54 is opened and the process proceeds to S55. In S55, the supply of hydrogen is started to eliminate the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, and then the normal operation routine is performed in S56.
  • According to the above-described sixth illustrated embodiment, the operation of the hydrogen gas circulation pump is started after the shutoff valve 54 provided downstream of the hydrogen circulation pump is closed. Therefore, if it is determined that hydrogen provided before the previous stoppage of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), the uneven distribution of hydrogen and oxygen in the fuel electrode 1b, which would otherwise occur immediately after the hydrogen circulation pump 24 is activated, can be avoided and the deterioration of the fuel cell can be prevented from progressing.
    • Seventh Embodiment
  • A fuel cell system according to a seventh embodiment of the present invention will be described below. The structure according to the seventh embodiment is similar to those shown in Figs. 1 and 16 except oxygen concentration meters and hydrogen concentration meters similar to the oxygen concentration meters 50 and 52 and the hydrogen concentration meter 51 and 53, respectively, are additionally provided in the hydrogen circulation pump 24 and at the outlet of the fuel cell body 1, as in the second to fourth embodiments.
    • Start Method
  • A method for starting the fuel cell system according to the seventh embodiment will be described below with reference to a flowchart shown in Fig. 18. When, for example, the state of a key switch is changed from Off to On, the controller 43 detects the change and follows the steps of the flowchart of Fig. 18 to start the fuel cell system.
  • First, in S61, it is determined whether or not the fuel chamber is filled with hydrogen that remains after the previous stoppage of power generation. If it is determined that the fuel chamber is filled with hydrogen in S61, that is, if the result of the determination of S62 is Yes, then it is determined that the fuel chamber is filled with hydrogen that remains after the previous stoppage of power generation (state A), that hydrogen and oxygen are not unevenly distributed in the fuel electrode 1b and that the deterioration of the fuel cell will not progress. Therefore, the process proceeds to S68 and the normal operation routine is performed.
  • If it is determined that the fuel chamber is not filled with hydrogen in S61, that is, if the result of the determination of S61 is No, then the process proceeds to S62, where it is determined whether or not the fuel chamber is filled with air that enters from the oxidizer electrode 1a (state B). If it is determined that the fuel chamber is filled with air in S62, that is, if the result of the determination of S62 is Yes, the uneven distribution of hydrogen and oxygen will not occur in the fuel electrode 1b even in the case where the hydrogen-circulation-pump discharge shutoff valve 54 is not closed. Therefore, the routine for closing the hydrogen-circulation-pump discharge shutoff valve 54 (S63) is skipped and the routine for operating the hydrogen circulation pump 24 is performed in S64.
  • If it is determined that the fuel chamber is not filled with air in S62, that is, if the result of the determination of S62 is No, then it is determined that hydrogen provided in the previous operation of power generation and air that enters from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C). Accordingly, the process proceeds to S63, where the hydrogen-circulation-pump discharge shutoff valve 54 is closed. S63 to S68 are similar to S51 to S56 according to the sixth embodiment, and explanations thereof are thus omitted.
  • The above-described embodiment provides the following effects:
    1. (1) If it is determined that the fuel electrode 1b is filled with hydrogen (state A), the normal power generating operation can be started immediately. Therefore, the start time can be reduced.
    2. (2) If it is determined that the fuel electrode 1b is filled with air (state B), the step of closing the hydrogen-circulation-pump discharge shutoff valve 54 is omitted. Therefore, the start time can be reduced.
    3. (3) If it is determined that hydrogen provided in the previous operation of power generation and air transmitted from the oxidizer electrode 1a are unevenly distributed in the fuel chamber (state C), an effect similar to that of the sixth embodiment can be obtained.
    Estimation of the air replacement state in the fuel chamber
  • In S61 and S62, the air replacement state in the fuel chamber is estimated on the basis of the time elapsed after the stoppage and the detection results of the oxygen concentration meters 50 and 52 and the hydrogen concentration meters 51 and 53 disposed in the hydrogen circulation pump 24 and at the outlet of the fuel cell body 1, similar to the first, second, third, fourth, and fifth embodiments.
  • In the above-described embodiments, the case in which the fuel cell system is stopped while the fuel electrode is in the hydrogen state and the air electrode is in the air state. However, the effects of the second to seventh embodiments may also be obtained when the fuel electrode and the air electrode are stopped in inert gas (the case in the fuel chamber is not completely filled with the inert gas and hydrogen remains in the fuel chamber).

Claims (23)

  1. A fuel cell system comprising:
    a fuel cell that includes a fuel electrode and an oxidizer electrode between which electrolyte is interposed, the fuel cell generating electric power when fuel gas and oxidizing gas are supplied to the fuel electrode and the oxidizer electrode, respectively;
    a fuel-gas circulation path that connects an inlet of the fuel electrode to an outlet of the fuel electrode, the fuel gas being supplied through the inlet and discharged from the outlet;
    a fuel-gas circulation pump provided on the fuel-gas circulation path;
    air replacement state recognizing means that estimates or detects a state in which hydrogen and air are unevenly distributed in at least one of the fuel electrode and the fuel-gas circulation path; and
    a start control device that operates the fuel-gas circulation pump after supplying the fuel gas upon starting the fuel cell if the air-replacement-state recognizing means estimates or detects that hydrogen and air are unevenly distributed , wherein the air replacement state recognizing means includes at least one of:
    - a timer
    - oxygen concentration sensor
    - a fuel-gas concentration sensor, being disposed at a portion, where replacement by air is finished first or last in the fuel electrode.
  2. The fuel cell system according to Claim 1, wherein the air replacement state recognizing means includes a timer for measuring the time that elapses after the fuel cell stops, and estimates that hydrogen and air are unevenly distributed when the elapsed time is more than a first predetermined time and less than a second predetermined time.
  3. The fuel cell system according to Claim 2, further comprising a thermometer that estimates or detects a temperature in the fuel cell, wherein the first and second predetermined times are corrected such that the first and second predetermined times are reduced as the temperature is increased.
  4. The fuel cell system according to Claim 2, wherein the supply of the fuel gas is started after the operation of the fuel-gas circulation pump is started if the elapsed time exceeds the second predetermined time.
  5. The fuel cell system according to Claim 2, wherein the supply of the fuel gas is started irrespective of whether or not the fuel-gas circulation pump is operated if the elapsed time is equal to or less than the first predetermined time.
  6. The fuel cell system according to Claim 1, wherein the air replacement state recognizing means includes an oxygen concentration sensor for detecting an oxygen concentration, the oxygen concentration sensor being disposed at a portion where replacement by air is finished last in the fuel electrode and the fuel-gas circulation path after the fuel cell stops, and
    wherein it is estimated that hydrogen and air are unevenly distributed if the oxygen concentration is less than a predetermined value.
  7. The fuel cell system according to Claim 1, wherein the air replacement state recognizing means includes a fuel- gas concentration sensor for detecting a fuel-gas concentration, the fuel-gas concentration sensor being disposed at a portion where replacement by air is finished last in the fuel electrode and the fuel-gas circulation path after the fuel cell stops, and
    wherein it is estimated that hydrogen and air are unevenly distributed if the fuel-gas concentration is more than a predetermined value.
  8. The fuel cell system according to Claim 1, wherein the air replacement state recognizing means includes an oxygen concentration sensor for detecting an oxygen concentration, oxygen concentration sensor being disposed at a portion where replacement by air is finished first in the fuel electrode and the fuel-gas circulation path after the fuel cell stops, and
    wherein the supply of the fuel gas is started irrespective of whether or not the fuel-gas circulation pump is started if the oxygen concentration is equal to or less than a predetermined value.
  9. The fuel cell system according to Claim 1, wherein the air replacement state recognizing means includes a fuel- gas concentration sensor for detecting a fuel-gas concentration, the fuel-gas concentration sensor being disposed at a portion where replacement by air is finished first in the fuel electrode and the fuel-gas circulation path after the fuel cell stops, and
    wherein the supply of the fuel gas is started irrespective of whether or not the fuel-gas circulation pump is operated if the fuel-gas concentration is equal to or more than a predetermined value.
  10. The fuel cell system according to Claim 1, further comprising a shutoff valve disposed between an outlet of the fuel-gas circulation pump and an inlet of a fuel cell body,
    wherein, if the air-replacement-state recognizing means estimates or detects that hydrogen and air are unevenly distributed, the operation of the fuel-gas circulation pump is started after the shutoff valve is closed, and then the shutoff valve is opened and the supply of the fuel gas is started when a rotational speed of the fuel-gas circulation pump becomes equal to or more than a predetermined value or when an inner pressure of the fuel electrode becomes equal to or less than a predetermined value.
  11. A method for starting up a fuel cell system, the fuel cell system comprising:
    a fuel cell that includes a fuel electrode and an oxidizer electrode between which electrolyte is interposed, the fuel cell generating electric power when fuel gas and oxidizing gas are supplied to the fuel electrode and the oxidizer electrode, respectively;
    a fuel-gas circulation path that connects an inlet of the fuel electrode to an outlet of the fuel electrode, the fuel gas being supplied through the inlet and discharged from the outlet; and
    a fuel-gas circulation pump provided on the fuel-gas circulation path, the method comprising the steps of:
    estimating or detecting a state in which hydrogen and air are unevenly distributed in at least one of the fuel electrode and the fuel-gas circulation path; and
    operating the fuel-gas circulation pump after supplying the fuel gas upon starting the fuel cell if it is estimated or detected that hydrogen and air are unevenly distributed.
  12. The method as in claim 11 wherein the step of estimating or detecting the state further comprises measuring a time since a previous stoppage of the fuel cell and when the measured time is greater than a first predetermined time but less than a second predetermined time, activating the fuel gas supply before the fuel-gas circulation pump.
  13. The method as in claim 12 further comprising when the measured time is equal to or greater than the second predetermined time greater than the first predetermined time, activating the fuel-gas circulation pump before the fuel gas supply.
  14. The method as in claim 11 wherein the step of estimating or detecting the state further comprises measuring an oxygen level within the fuel-gas circulation pump and when the measured level is greater than or equal to a predetermined oxygen level, activating the fuel-gas circulation pump before the fuel gas supply.
  15. The method as in claim 14 further comprising when the measured level is less than the predetermined oxygen level, activating the fuel gas supply before the fuel-gas circulation pump.
  16. The method as in claim 11 wherein the step of estimating or detecting the state further comprises measuring a hydrogen level within the fuel-gas circulation pump and when the measured level is equal to or less than a first predetermined hydrogen level, activating the fuel-gas circulation pump before the fuel gas supply.
  17. The method as in claim 16 further comprising when the measured level is greater than the predetermined hydrogen level, activating the fuel gas supply before the fuel-gas circulation pump.
  18. The method as in claim 11 wherein the step of estimating or detecting the state further comprises measuring an oxygen level proximate an outlet of the fuel electrode and when the measured level is equal to or less than a predetermined oxygen level, activating the fuel-gas circulation pump and the fuel gas supply substantially simultaneously.
  19. The method as in claim 18 further comprising when the measured level is more than the predetermined oxygen level, activating the fuel gas supply before the fuel-gas circulation pump.
  20. The method as in claim 11 wherein the step of estimating or detecting the state further comprises measuring a hydrogen level proximate an outlet of the fuel electrode and when the measured level is equal to or more than a predetermined hydrogen level, activating the fuel-gas circulation pump and the fuel gas supply substantially simultaneously.
  21. The method as in claim 20 further comprising when the measured level is less than the predetermined hydrogen level, activating the fuel gas supply before the fuel-gas circulation pump.
  22. The method as in claim 11 further comprising disposing a valve that blocks on outlet of the fuel-gas circulation pump in the fuel-gas circulation path, activating the fuel-gas circulation pump, measuring a rotational speed of the fuel-gas circulation pump and when the measured speed is equal to or more than a predetermined speed, opening the valve and activating the fuel gas supply.
  23. A fuel cell system comprising:
    a fuel cell that includes a fuel electrode and an oxidizer electrode between which electrolyte is interposed, the fuel cell generating electric power when fuel gas and oxidizing gas are supplied to the fuel electrode- and the oxidizer electrode, respectively;
    a fuel-gas circulation path that connects an inlet of the fuel electrode to an outlet of the fuel electrode, the fuel gas being supplied through the inlet and discharged from the outlet;
    a fuel-gas circulation pump provided on the fuel-gas circulation path;
    a valve between an outlet of the fuel-gas circulation pump and an inlet of the fuel electrode; and
    a controller configured to:
    - detect start of the fuel cell system,
    - close the valve when detecting start of the fuel cell system,
    - detect that the fuel-gas circulation pump reaches a predetermined speed, and
    - open the valve when detecting that the fuel-gas circulation pump reaches a predetermined speed.
EP06851562A 2006-12-27 2006-12-27 Fuel cell system Not-in-force EP2132819B1 (en)

Applications Claiming Priority (1)

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PCT/IB2006/004310 WO2008093147A2 (en) 2006-12-27 2006-12-27 Fuel cell system

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EP2132819A2 EP2132819A2 (en) 2009-12-16
EP2132819B1 true EP2132819B1 (en) 2012-05-02

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EP2132819A2 (en) 2009-12-16
ATE556455T1 (en) 2012-05-15
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WO2008093147A2 (en) 2008-08-07
US8338042B2 (en) 2012-12-25

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